US3954484A - Fluorophosphate glass and process of making same - Google Patents
Fluorophosphate glass and process of making same Download PDFInfo
- Publication number
- US3954484A US3954484A US05/499,661 US49966174A US3954484A US 3954484 A US3954484 A US 3954484A US 49966174 A US49966174 A US 49966174A US 3954484 A US3954484 A US 3954484A
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- United States
- Prior art keywords
- fluoride
- metaphosphate
- component
- barium
- mixture
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- 239000005303 fluorophosphate glass Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 230000002547 anomalous effect Effects 0.000 claims abstract description 13
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 94
- 239000000203 mixture Substances 0.000 claims description 64
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 60
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 56
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 55
- 239000011521 glass Substances 0.000 claims description 41
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 38
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 38
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 claims description 38
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 38
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 38
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 34
- 125000005341 metaphosphate group Chemical group 0.000 claims description 33
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 30
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 28
- 239000011777 magnesium Substances 0.000 claims description 24
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 claims description 20
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 19
- 229910002319 LaF3 Inorganic materials 0.000 claims description 19
- XNJIKBGDNBEQME-UHFFFAOYSA-L barium(2+);dioxido(oxo)phosphanium Chemical compound [Ba+2].[O-][P+]([O-])=O.[O-][P+]([O-])=O XNJIKBGDNBEQME-UHFFFAOYSA-L 0.000 claims description 19
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 19
- RHJYKEDKMHDZBL-UHFFFAOYSA-L metaphosphoric acid (hpo3), magnesium salt Chemical compound [Mg+2].[O-]P(=O)=O.[O-]P(=O)=O RHJYKEDKMHDZBL-UHFFFAOYSA-L 0.000 claims description 19
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 15
- 150000002222 fluorine compounds Chemical class 0.000 claims description 15
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 229940119177 germanium dioxide Drugs 0.000 claims description 13
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 16
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims 2
- 230000003287 optical effect Effects 0.000 description 6
- 239000010955 niobium Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 for instance Substances 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S501/00—Compositions: ceramic
- Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
- Y10S501/903—Optical glass, e.g. silent on refractive index and/or ABBE number having refractive index less than 1.8 and ABBE number less than 70
Definitions
- the present invention relates to a process of producing a fluorophosphate glass and more particularly to a process of producing a fluorophosphate glass having an index of refraction n e of more than 1.57 and an Abbe number ⁇ e of less than 70, said glass having furthermore a relatively high positive anomalous partial dispersion + ⁇ e , and to such a glass.
- U.S. Pat. No. 3,492,136 a process for the manufacture of a fluorophosphate glass the starting mixture of which, in addition to calcium and/or aluminum metaphosphate, also contains alkaline earth metal fluorides and one of the compounds potassium meta-arsenate, potassium heptafluoro tantalate, or, respectively, potassium hexafluoro titanate.
- the glass produced by this known process have indices of refraction n e between 1.53 and 1.55. Such indices must be considered relatively high for this type of glass.
- U.S. Pat. No. 3,671,276 discloses an improvement in the process described in U.S. Pat. No. 3,492,136 by which fluorophosphate glasses having indices of refraction n e between 1.50 and 1.56 can be produced.
- optical fluorophosphate glasses of medium to low dispersion -- corresponding to a medium to high Abbe number ⁇ e -- and of indices of refraction n e between 1.53 and 1.56.
- Such glasses furthermore, exhibit a positive anomalous partial dispersion + ⁇ e .
- Another object of the present invention is to provide a process of producing such glasses with a high index of refraction, a low Abbe number, and a high positive anomalous partial dispersion.
- magnesium fluoride MgF 2 0.1 % to 1.5 %
- germanium dioxide GeO 2 up to 10.0 % of germanium dioxide GeO 2 ,
- niobium pentoxide Nb 2 O 5 up to 20.0 % of niobium pentoxide Nb 2 O 5 .
- magnesium metaphosphate Mg(PO 3 ) 2 4.0 % to 23.0 % of magnesium metaphosphate Mg(PO 3 ) 2 ,
- niobium pentoxide Nb 2 O 5 up to 18.0 % of niobium pentoxide Nb 2 O 5 .
- the mixture of glass components to yield a glass of the present invention may consist of the following agents, in weight percent:
- magnesium metaphosphate Mg(PO 3 ) 2 4.5 % to 22.5 % of magnesium metaphosphate Mg(PO 3 ) 2 ,
- the total amount of the metaphosphates used not being less than 28.6 % and not exceeding 46.6 %;
- germanium dioxide GeO 2 up to 7.5 % of germanium dioxide GeO 2
- niobium pentoxide Nb 2 O 5 up to 18.0 % of niobium pentoxide Nb 2 O 5 .
- FIG. 1 shows the optical position range of the glasses produced by the process of the present invention in an n e - ⁇ e diagram as compared with known glasses
- FIG. 2 shows the optical position range of the glasses produced by the process of the present invention in a ⁇ ' g - ⁇ e diagram.
- Fluorophosphate glasses according to the present invention are produced, for instance, by melting mixtures composed as listed in the following Table but not limited to the amounts of components as given therein. The amounts given in the Table are amounts in weight percent.
- glasses having high refraction values n e > 1.57 and Abbe numbers ⁇ e between 70 and 41 are obtained.
- Such glasses retain surprisingly relatively high positive anomalous partial dispersion values + ⁇ e due to providing, in addition to metaphosphates, also fluorides of bivalent or trivalent metals and oxides of bivalent to pentavalent elements as components of the mixtures in the ranges indicated and claimed hereinafter.
- the graph illustrated in FIG. 1 shows the index of refraction n e plotted on the ordinate and the Abbe number ⁇ e plotted on the abscissa.
- the glasses according to the present invention are indicated by a small solid triangle.
- the glasses of U.S. Pat. No. 3,492,136 are marked by a solid circle and the glasses of U.S. Pat. No. 3,671,276 are marked by a hollow circle. It is evident that all the examples of glasses according to this invention lie outside those regions of the n e - ⁇ e field which are covered by the glasses disclosed in said two U.S. patents.
- the glasses of the present invention show, without any exception, higher n e values and in general also lower Abbe numbers.
- the third important optical parameter of the fluorophosphate glasses namely the positive anomalous partial dispersion value + ⁇ e
- the ⁇ ' g value is plotted as ordinate and the Abbe number ⁇ e again as abscissa.
- the following example serves to illustrate the manner in which the glass according to the present invention is produced by melting down a mixture of its components.
- a well mixed charge, in weight percent, of the following composition is provided:
- the mixture is melted in amounts of 2.5 kg. in a platinum crucible at 1000° C. Thereafter, the melting temperature is increased by about 100° C. to 1100° C. The melt is refined and homogenized at said temperature for 10 to 15 minutes. Thereupon, it is allowed to cool to 800° C. by discontinuing heat supply, while stirring, and is then poured into aluminum molds preheated to 530° C.
- the temperatures of melting, refining and homogenizing, cooling, and casting the glass component mixture may vary by ⁇ 5 %.
- additives customarily added in glass technology to the batches of glass component mixtures for instance, additives for refining of the melt, such as alkali metal meta-arsenates, arsenates, bifluorides, and others in amounts not exceeding about 3 %, by weight, can be added to the glass component mixture without exceeding or substantially varying the scope of the present invention.
- Mixtures containing such additives which are within the scope of the attached claims thus are also comprised by them.
- the temperature-time program as given hereinabove for carrying out the melting procedure represents also merely an example.
- the melting process can, of course, be modified by a person skilled in the art, depending on the specific charges of glass components employed.
- the glasses according to the present invention are especially useful in apochromatically corrected objectives for microscopes and photographic apparatus, especially in telephoto lens systems.
- spectral wavelengths or spectral lines e, g, F', and C' of the equations given hereinabove are, respectively, the following lines:
- g blue mercury line of the wavelength of 435.84 nm.
- F' blue cadmium line of the wavelength of 479.99 nm.
- C' red cadmium line of the wavelength of 643.85 nm.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
A fluorophosphate glass which has an index of refraction ne of more than 1.57, an Abbe number nu e of less than 70, and a relatively high positive anomalous partial dispersion + DELTA nu e is provided.
Description
1. Field of the Invention
The present invention relates to a process of producing a fluorophosphate glass and more particularly to a process of producing a fluorophosphate glass having an index of refraction ne of more than 1.57 and an Abbe number νe of less than 70, said glass having furthermore a relatively high positive anomalous partial dispersion +Δνe, and to such a glass.
2. Description of the Prior Art
It is known to produce, by melting, glasses being based on metaphosphates of Group II and Group III of the periodic system with the addition of simple and/or complex inorganic fluorides, said glasses having a positive anomalous partial dispersion.
Thus there is known from U.S. Pat. No. 3,492,136 a process for the manufacture of a fluorophosphate glass the starting mixture of which, in addition to calcium and/or aluminum metaphosphate, also contains alkaline earth metal fluorides and one of the compounds potassium meta-arsenate, potassium heptafluoro tantalate, or, respectively, potassium hexafluoro titanate. The glass produced by this known process have indices of refraction ne between 1.53 and 1.55. Such indices must be considered relatively high for this type of glass. Furthermore, U.S. Pat. No. 3,671,276 discloses an improvement in the process described in U.S. Pat. No. 3,492,136 by which fluorophosphate glasses having indices of refraction ne between 1.50 and 1.56 can be produced.
Thus according to these known processes it was possible to produce optical fluorophosphate glasses of medium to low dispersion -- corresponding to a medium to high Abbe number νe -- and of indices of refraction ne between 1.53 and 1.56. Such glasses, furthermore, exhibit a positive anomalous partial dispersion +Δνe.
It is, however, of interest with respect to certain fields of use in the optical industry to provide glasses of even higher refractive values ne >1.57 and of optimum dispersion, but which meet the requirements of the calculating optician, namely requiring that such glasses also retain, or at least only slightly reduce, their positive anomalous partial dispersion values. Such glasses, heretofore, have not been produced.
It is one object of the present invention to provide glasses having not only an index of refraction ne which exceeds the index of 1.57 and an Abbe number νe lower than 70, but also having a relatively high positive anomalous partial dispersion +Δνe.
Another object of the present invention is to provide a process of producing such glasses with a high index of refraction, a low Abbe number, and a high positive anomalous partial dispersion.
Other objects of the present invention and advantageous features thereof will become apparent as the description proceeds.
In principle these objects are achieved in accordance with the present invention by producing glasses by melting a glass component mixture of the following components, in weight percent:
0.1 % to 1.5 % of magnesium fluoride MgF2,
0.1 % to 1.5 % of calcium fluoride CaF2,
up to 15.0 % of strontium fluoride SrF2,
up to 25.0 % of barium fluoride BaF2,
up to 10.0 % of aluminum fluoride AlF3, and
0.1 % to 1.5 % of lanthanum fluoride LaF3,
the total amount of the alkaline earth metal fluorides to be used not exceeding about 38 % and the total amount of all the fluorides used not exceeding about 45 %;
8.0 % to 12.0 % of aluminum metaphosphate Al(PO3)3,
3.0 % to 25.0 % of magnesium metaphosphate Mg(PO3)2,
10.0 % to 18.0 % of barium metaphosphate Ba(PO3)2,
the total amount of the metaphosphates used not exceeding about 50 %;
8.0 % to 55.0 % of barium oxide BaO;
up to 17.0 % of boron trioxide B2 O3,
up to 10.0 % of germanium dioxide GeO2,
up to 4.0 % of titanium dioxide TiO2, and
up to 20.0 % of niobium pentoxide Nb2 O5.
It is also possible to produce glasses according to the present invention by melting a mixture consisting of the following components, in weight percent:
0.4 % to 0.5 % of magnesium fluoride MgF2,
0.5 % to 0.6 % of calcium fluoride CaF2,
up to 13.0 % of strontium fluoride SrF2,
up to 22.0 % of barium fluoride BaF2,
up to 8.0 % of aluminum fluoride AlF3, and
0.5 % to 0.6 % of lanthanum fluoride LaF3,
the total amount of the alkaline earth metal fluorides to be used not exceeding about 35 % and the total amount of all the fluorides used not exceeding about 43 %;
9.0 % to 10.0 % of aluminum metaphosphate Al(PO3)3,
4.0 % to 23.0 % of magnesium metaphosphate Mg(PO3)2,
11.0 % to 15.0 % of barium metaphosphate Ba(PO3)2,
the total amount of the metaphosphates used not exceeding about 47 %;
10.0 % to 52.0 % of barium oxide BaO;
up to 15.0 % boron trioxide B2 O3,
up to 8.0 % of germamium dioxide GeO2,
up to 2.0 % of titanium dioxide TiO2, and
up to 18.0 % of niobium pentoxide Nb2 O5.
According to a preferred embodiment of the present invention the mixture of glass components to yield a glass of the present invention may consist of the following agents, in weight percent:
0.44 % of magnesium fluoride MgF2,
0.53 % of calcium fluoride CaF2,
up to 12.2 % of strontium fluoride SrF2,
up to 21.5 % of barium fluoride BaF2,
up to 7.5 % of aluminum fluoride AlF3,
0.53 % of lanthanum fluoride LaF3,
the total amount of the alkaline earth metal fluorides used not being less than 0.97 % and not exceeding 34.67 %, and the total amount of all the fluorides used not being less than 1.5 % and not exceeding 42.7 %;
9.3 % of aluminum metaphosphate Al(PO3)3,
4.5 % to 22.5 % of magnesium metaphosphate Mg(PO3)2,
11.8 % to 14.8 % of barium metaphosphate Ba(PO3)2,
the total amount of the metaphosphates used not being less than 28.6 % and not exceeding 46.6 %;
10.7 % to 51.9 % of barium oxide BaO;
up to 15.0 % of boron trioxide B2 O3,
up to 7.5 % of germanium dioxide GeO2,
up to 1.5 % of titanium dioxide TiO2, and
up to 18.0 % of niobium pentoxide Nb2 O5.
In the accompanying drawings, the particular optical parameters of glasses produced according to the present invention are shown. In said drawings:
FIG. 1 shows the optical position range of the glasses produced by the process of the present invention in an ne -νe diagram as compared with known glasses, and
FIG. 2 shows the optical position range of the glasses produced by the process of the present invention in a θ'g -νe diagram.
Fluorophosphate glasses according to the present invention are produced, for instance, by melting mixtures composed as listed in the following Table but not limited to the amounts of components as given therein. The amounts given in the Table are amounts in weight percent.
Melt No.:
1 2 3 4 5 6 7 8 9
__________________________________________________________________________
Mg(PO.sub.3).sub.2
22.50
22.50
22.50
22.50
22.50
22.50
22.50
22.50
22.50
Ba(PO.sub.3).sub.2
14.80
14.80
14.80
14.80
14.80
14.80
14.80
14.80
14.80
Al(PO.sub.3).sub.3
9.30
9.30 9.30 9.30 9.30 9.30 9.30 9.30 9.30
MgF.sub.2
0.44
0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44
CaF.sub.2
0.53
0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53
SrF.sub.2
12.20
12.20
12.20
12.20
12.20
12.20
12.20
12.20
9.20
BaF.sub.2
21.50
18.50
15.50
12.50
9.50 6.50 3.50 -- --
AlF.sub.3
7.50
7.50 7.50 7.50 7.50 7.50 7.50 7.50 7.50
LaF.sub.3
0.53
0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53
BaO 10.70
13.70
16.70
19.70
22.70
25.70
28.70
32.20
35.20
B.sub.2 O.sub.3
-- -- -- -- -- -- -- -- --
GeO.sub.2
-- -- -- -- -- -- -- -- --
TiO.sub.2
-- -- -- -- -- -- -- -- --
Nb.sub.2 O.sub.5
-- -- -- -- -- -- -- -- --
__________________________________________________________________________
n.sub.e
1.5753
1.5763
1.5766
1.5781
1.5801
1.5820
1.5845
1.5878
1.5928
ν.sub.e
69.6
69.6 69.7 69.5 68.8 68.7 68.8 68.4 67.6
Δν.sub.e
+10.9
+10.4
+10.6
+9.3 +6.6 +8.2 +8.1 +9.0 +7.0
θ'.sub.g
0.4836
0.4828
0.4833
0.4814
0.4786
0.4808
0.4808
0.4825
0.4809
__________________________________________________________________________
Melt No.:
10 11 12 13 14 15 16 17 18 15a
__________________________________________________________________________
Mg(PO.sub.3).sub.2
22.50
22.50
22.50
22.50
22.50
22.50
22.50
22.50
22.50
22.50
Ba(PO.sub.3).sub.2
14.80
14.80
14.80
14.80
14.80
14.80
14.80
14.80
14.80
14.80
Al(PO.sub.3).sub.3
9.30
9.30 9.30 9.30 9.30 9.30 9.30 9.30 9.30 9.30
MgF.sub.2
0.44
0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44
CaF.sub.2
0.53
0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53
SrF.sub.2
6.20
3.20 -- -- -- -- 12.20
12.20
12.20
--
BaF.sub.2
-- -- -- -- -- -- -- -- -- --
AlF.sub.3
7.50
7.50 7.50 4.50 2.00 -- 7.50 7.50 7.50 1.00
LaF.sub.3
0.53
0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53
BaO 38.20
41.20
44.40
47.40
49.90
51.90
31.70
31.20
30.70
50.90
B.sub.2 O.sub.3
-- -- -- -- -- -- -- -- -- --
GeO.sub.2
-- -- -- -- -- -- -- -- -- --
TiO.sub.2
-- -- -- -- -- -- 0.50 1.00 1.50 --
Nb.sub.2 O.sub.5
-- -- -- -- -- -- -- -- -- --
__________________________________________________________________________
n.sub.e
1.5963
1.6012
1.6073
1.6175
1.6267
-- 1.5926
1.5931
1.5986
1.6107
ν.sub.e
67.2
66.4 65.7 64.3 62.7 -- 65.7 63.7 61.4 64.65
Δν.sub.e
+6.9
+7.5 +5.5 +6.1 +5.6 -- + 9.1
+8.7 +8.3 +9.5
θ'.sub.g
0.4813
0.4833
0.4815
0.4843
0.4859
-- 0.4866
0.4888
0.4916
0.4887
__________________________________________________________________________
Melt No.:
19 20 21 22 23 24 25 26 27
__________________________________________________________________________
Mg(PO.sub.3).sub.2
22.50
22.50
22.50
22.50
19.50
16.50
13.50
10.50
7.50
Ba(PO.sub.3).sub.2
14.80
14.80
14.80
14.80
14.80
14.80
14.80
14.80
14.80
Al(PO.sub.3).sub.2
9.30
9.30 9.30 9.30 9.30 9.30 9.30 9.30 9.30
MgF.sub.2
0.44
0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44
CaF.sub.2
0.53
0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53
SrF.sub.2
12.20
12.20
12.20
12.20
12.20
12.20
12.20
12.20
12.20
BaF.sub.2
-- -- -- -- -- -- -- -- --
AlF.sub.3
7.50
7.50 7.50 7.50 7.50 7.50 7.50 7.50 7.50
LaF.sub.3
0.53
0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53
BaO 29.20
26.20
27.70
29.20
32.20
32.20
32.20
32.20
32.20
B.sub.2 O.sub.3
-- -- -- -- -- -- -- -- --
GeO.sub. 2
3.00
6.00 4.50 -- -- -- -- -- --
TiO.sub.2
-- -- -- -- -- -- -- -- --
Nb.sub.2 O.sub.5
-- -- -- 3.00 3.00 6.00 9.00 12.00
15.00
__________________________________________________________________________
n.sub.e
1.5915
1.5934
1.5922
1.5974
1.6005
1.6130
1.6285
1.6473
1.6676
ν.sub.e
67.7
67.1 67.2 62.7 62.2 57.5 53.0 48.8 45.0
Δν.sub.e
+9.5
+10.2
+6.5 +5.1 +6.2 +5.6 +4.8 +6.3 +6.5
θ'.sub.g
0.4843
0.4862
0.4807
0.4852
0.4874
0.4932
0.4999
0.5066
0.5123
__________________________________________________________________________
Melt No.:
28 29 30 31 32 33 34 35 34a 35a
__________________________________________________________________________
Mg(PO.sub.3).sub.2
4.50
7.50 19.50
19.50
16.50
13.50
10.50
7.50 13.50
13.50
Ba(PO.sub.3).sub.2
14.80
11.80
14.80
14.80
14.80
14.80
14.80
14.80
14.80
14.80
Al(PO.sub.3).sub.2
9.30
9.30 9.30 9.30 9.30 9.30 9.30 9.30 9.30 9.30
MgF.sub.2
0.44
0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44
CaF.sub.2
0.53
0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53
SrF.sub.2
12.20
12.20
12.20
12.20
12.20
12.20
12.20
12.20
9.20 6.20
BaF.sub.2
-- -- -- -- -- -- -- -- -- --
AlF.sub.3
7.50
7.50 7.50 7.50 7.50 7.50 7.50 7.50 7.50 7.50
LaF.sub.3
0.53
0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53
BaO 32.20
32.20
27.70
32.20
32.20
32.20
32.20
32.20
32.20
32.20
B.sub.2 O.sub.3
-- -- -- 3.00 6.00 9.00 12.00
15.00
12.00
15.00
GeO.sub.2
-- -- 7.50 -- -- -- -- -- -- --
TiO.sub.2
-- -- -- -- -- -- -- -- -- --
Nb.sub.2 O.sub.5
18.00
18.00
-- -- -- -- -- -- -- --
__________________________________________________________________________
n.sub.e
1.6910
1.6915
1.5949
1.6031
1.6049
1.6055
-- -- 1.6077
1.6056
41.5.41.2.65.8 66.2
766.4 65.9 -- -- 64
.08 64.52
Δν.sub.e
+5.2
+6.4 +5.5 +6.6 + 8.9
+5.0 -- -- +4.5 +3.5
θ'.sub.g
0.5155
0.5175
0.4812
0.4823
0.4881
0.4803
-- -- 0.4823
0.4801
__________________________________________________________________________
As shown by the examples given in the Table, glasses having high refraction values ne > 1.57 and Abbe numbers νe between 70 and 41 are obtained. Such glasses retain surprisingly relatively high positive anomalous partial dispersion values +Δνe due to providing, in addition to metaphosphates, also fluorides of bivalent or trivalent metals and oxides of bivalent to pentavalent elements as components of the mixtures in the ranges indicated and claimed hereinafter.
The graph illustrated in FIG. 1 shows the index of refraction ne plotted on the ordinate and the Abbe number νe plotted on the abscissa. In said graph the glasses according to the present invention are indicated by a small solid triangle. Compared therewith the glasses of U.S. Pat. No. 3,492,136 are marked by a solid circle and the glasses of U.S. Pat. No. 3,671,276 are marked by a hollow circle. It is evident that all the examples of glasses according to this invention lie outside those regions of the ne -νe field which are covered by the glasses disclosed in said two U.S. patents. The glasses of the present invention show, without any exception, higher ne values and in general also lower Abbe numbers.
In the two-dimensional graphical showing of FIG. 1 the third important optical parameter of the fluorophosphate glasses, namely the positive anomalous partial dispersion value +Δνe, can, of course, not be taken into consideration. Said value becomes evident from FIG. 2. In the graph of said FIG. 2 the θ'g value is plotted as ordinate and the Abbe number νe again as abscissa.
The following mathematical relationship applies to the two values θ'g and νe : ##EQU1##
In said equations the subscripts e, g, F', and C' stand for concrete standard wavelengths.
The symbols used in FIG. 2 correspond to those used in FIG. 1. It is evident that all the glasses of the present invention lie to the right of the so-called "standard straight line". They, therefore, all have a positive Δνe, i.e. a +Δνe glass has a higher νe value than a "standard" glass.
The following example serves to illustrate the manner in which the glass according to the present invention is produced by melting down a mixture of its components.
A well mixed charge, in weight percent, of the following composition is provided:
Mg(PO.sub.3).sub.2
22.50 %
Ba(PO.sub.3).sub.2
14.80 %
Al(PO.sub.3).sub.3
9.30 %
MgF.sub.2 0.44 %
CaF.sub.2 0.53 %
SrF.sub.2 12.20 %
AlF.sub.3 7.50 %
LaF.sub.3 0.53 %
BaO 32.20 %
The mixture is melted in amounts of 2.5 kg. in a platinum crucible at 1000° C. Thereafter, the melting temperature is increased by about 100° C. to 1100° C. The melt is refined and homogenized at said temperature for 10 to 15 minutes. Thereupon, it is allowed to cool to 800° C. by discontinuing heat supply, while stirring, and is then poured into aluminum molds preheated to 530° C. The temperatures of melting, refining and homogenizing, cooling, and casting the glass component mixture may vary by ±5 %.
It is to be pointed out that additives customarily added in glass technology to the batches of glass component mixtures, for instance, additives for refining of the melt, such as alkali metal meta-arsenates, arsenates, bifluorides, and others in amounts not exceeding about 3 %, by weight, can be added to the glass component mixture without exceeding or substantially varying the scope of the present invention. Mixtures containing such additives which are within the scope of the attached claims thus are also comprised by them.
The temperature-time program as given hereinabove for carrying out the melting procedure represents also merely an example. The melting process can, of course, be modified by a person skilled in the art, depending on the specific charges of glass components employed.
The glasses according to the present invention are especially useful in apochromatically corrected objectives for microscopes and photographic apparatus, especially in telephoto lens systems.
It may be pointed out that the spectral wavelengths or spectral lines e, g, F', and C' of the equations given hereinabove are, respectively, the following lines:
e = green mercury line of the wavelength of 546.07 nm.
g = blue mercury line of the wavelength of 435.84 nm.
F' = blue cadmium line of the wavelength of 479.99 nm.
C' = red cadmium line of the wavelength of 643.85 nm.
Claims (24)
1. In a process of producing a fluorophosphate glass having an index of refraction ne within the range of from about 1.5753 to about 1.6915, an Abbe number νe within the range of from about 41.2 to 69.7, and a relatively high positive anomalous partial dispersion, comprising the steps of
a. melting a mixture essentially consisting of the following components, in weight percent:
Fluoride component (a)
0.1% to 1.5% of magnesium fluoride MgF2,
0.1% to 1.5% of calcium fluoride CaF2,
0% to 15.0% of strontium fluoride SrF2,
0% to 25.0% of barium fluoride BaF2,
0% to 10.0% of aluminum fluoride AlF3, and
0.1% to 1.5% of lanthanum fluoride LaF3,
the total sum of the alkaline earth metal fluorides in said mixture not exceeding 38% and the total sum of all fluorides in said mixture not exceeding 45%.
Metaphosphate component (b)
8.0% to 12.0% of aluminum metaphosphate Al(PO3)2,
3.0% to 25.0% of magnesium metaphosphate Mg(PO3)2, and
10.0% to 18.0% of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture not exceeding 50%;
Barium oxide component (c)
8. 0% to 55.0% of barium oxide BaO;
Additional oxide component (d)
0% to 17.0% of boron trioxide B2 O3,
0% to 10.0% of germanium dioxide GeO2,
0% to 4.0% of titanium dioxide TiO2, and
0% to 20.0% of niobium pentoxide Nb2 O5 ;
b. homogenizing the molten mixture at a temperature within the range of from about 1000°C. to about 1100°C. with stirring;
c. cooling said molten mixture to about 800°C.; and,
d. pouring said mixture into preheated molds.
2. The process of claim 1, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0.4 % to 0.5 % of magnesium fluoride MgF2,
0.5 % to 0.6 % of calcium fluoride CaF2,
0 % to 13.0 % of strontium fluoride SrF2,
0 % to 22.0 % of barium fluoride BaF2,
0 % to 8.0 % of aluminum fluoride AlF3, and
0.5 % to 0.6 % of lanthanum fluoride LaF3 ;
the total sum of the alkaline earth metal fluorides in said mixture not exceeding the sum of 35 % and the total sum of all fluorides not exceeding 43 %;
Metaphosphate component (b)
9.0 % to 10.0 % of aluminum metaphosphate Al(PO3)3,
4.0 % to 23.0 % of magnesium metaphosphate Mg(PO3)2, and
11.0 % to 15.0 % of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture not exceeding 47 %;
Barium oxide component (c)
10.0 % to 52.0 % of barium oxide BaO; and
Additional oxide component (d)
0 % to 15.0 % of boron trioxide B2 O3,
0 % to 8.0 % of germanium dioxide GeO2,
0 % to 2.0 % of titanium dioxide TiO2, and
0 % to 18.0 % of niobium pentoxide Nb2 O5.
3. The process of claim 1 in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0. 44 % of magnesium fluoride MgF2,
0.53 % of calcium fluoride CaF2,
0 % to 12.2 % of strontium fluoride SrF2,
0 % to 21.5 % of barium fluoride BaF2,
0 % to 7.5 % of aluminum fluoride AlF3, and
0.53 % of lanthanum fluoride LaF3,
the total sum of the alkaline earth metal fluorides being at least 0.97 % and not exceeding 34.67 % and the total sum of all fluorides in said mixture being at least 1.5 % and not exceeding 42.7 %;
Metaphosphate component (b)
9.3 % of aluminum metaphosphate Al(PO3)3,
4.5 % to 22.5 % of magnesium metaphosphate Mg(PO3)2, and
11.8 % to 14.8 % of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture being at least 28.6 % and not exceeding 46.6 %;
Barium oxide component (c)
10.7 % to 51.9 % of barium oxide BaO; and
Additional oxide component (d)
0 % to 15.0 % of boron trioxide B2 O3,
0 % to 7.5 % of germanium dioxide GeO2,
0 % to 1.5 % of titanium dioxide TiO2, and
0 % to 18.0 % of niobium pentoxide Nb2 O5.
4. A batch composition for making fluorophosphate glass having an index of refraction ne within the range of from about 1.5753 to about 1.6915, an Abbe number νe within the range of from about 41.2 to 69.7, and a relatively high positive anomalous partial dispersion, said composition essentially consisting of the following components, in weight percent:
Fluoride component (a)
0.1% to 1.5% of magnesium fluoride MgF2,
0.1% to 1.5% of calcium fluoride CaF2,
0% to 15.0% of strontium fluoride SrF2,
0% to 25.0% of barium fluoride BaF2,
0% to 10.0% of aluminum fluoride AlF3, and
0.1% to 1.5% of lanthanum fluoride LaF3,
the total sum of the alkaline earth metal fluorides in said mixture not exceeding 38% and the total sum of all fluorides in said mixture not exceeding 45%;
Metaphosphate component (b)
8.0% to 12% of aluminum metaphosphate Al(PO3)2,
3.0% to 25.0% of magnesium metaphosphate Mg(PO3)2, and
10.0% to 18.0% of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture not exceeding 50%;
Barium oxide component (c)
8.0% to 55.0% of barium oxide BaO;
Additional oxide component (d)
0% to 17.0% of boron trioxide B2 O3,
0% to 10.0% of germanium dioxide GeO2,
0% to 4.0% of titanium dioxide TiO2, and
0% to 20.0% of niobium pentoxide Nb2 O5.
5. The composition of claim 4, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0. 4 % to 0.5 % of magnesium fluoride MgF2,
0.5 % to 0.6 % of calcium fluoride CaF2,
0 % to 13.0 % of strontium fluoride SrF2,
0 % to 22.0 % of barium fluoride BaF2,
0 % to 8.0 % of aluminum fluoride AlF3, and
0.5 % to 0.6 % of lanthanum fluoride LaF3 ;
the total sum of the alkaline earth metal fluorides in said mixture not exceeding the sum of 35 % and the total sum of all fluorides not exceeding 43 %;
Metaphosphate component (b)
9.0 % to 10.0 % of aluminum metaphosphate Al(PO3)3,
4.0 % to 23.0 % of magnesium metaphosphate Mg(PO3)2, and
11.0 % to 15.0 % of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture not exceeding 47 %;
Barium oxide component (c)
10.0 % to 52.0 % of barium oxide BaO; and
Additional oxide component (d)
0 % to 15.0 % of boron trioxide B2 O3,
0 % to 8.0 % of germanium dioxide GeO2,
0 % to 2.0 % of titanium dioxide TiO2, and
0 % to 18.0 % of niobium pentoxide Nb2 O5.
6. The composition of claim 4, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0. 44 % of magnesium fluoride MgF2,
0.53 % of calcium fluoride CaF2,
0 % to 12.2 % of strontium fluoride SrF2,
0 % to 21.5 % of barium fluoride BaF2,
0 % to 7.5 % of aluminum fluoride AlF3, and
0.53 % of lanthanum fluoride LaF3,
the total sum of the alkaline earth metal fluorides being at least 0.97 % and not exceeding 34.67 % and the total sum of all fluorides in said mixture being at least 1.5 % and not exceeding 42.7 %;
Metaphosphate component (b)
9.3 % of aluminum metaphosphate Al(PO3)3,
4.5 % to 22.5 % of magnesium metaphosphate Mg(PO3)2, and
11.8 % to 14.8 % of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture being at least 28.6 % and not exceeding 46.6 %;
Barium oxide component (c)
10.7 % to 51.9 % of barium oxide BaO; and
Additional oxide component (d)
0 % to 15.0 % of boron trioxide B2 O3,
0 % to 7.5 % of germanium dioxide GeO2,
0 % to 1.5 % of titanium dioxide TiO2, and
0 % to 18.0 % of niobium pentoxide Nb2 O5.
7. The composition of claim 4, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0.44 % of magnesium fluoride MgF2,
0.53 % of calcium fluoride CaF2,
12.20 % of strontium fluoride SrF2,
7.50 % of aluminum fluoride AlF3, and
0.53 % of lanthanum fluoride LaF3 ;
Metaphosphate component (b)
9.30 % of aluminum metaphosphate Al(PO3)3,
22.50 % of magnesium metaphosphate Mg(PO3)2, and
14.80 % of barium metaphosphate Ba(PO3)2 ; and
Barium oxide component (c)
32.20 % of barium oxide BaO.
8. The composition of claim 4, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0.44 % of magnesium fluoride MgF2,
0.53 % of calcium fluoride CaF2,
12.20 % of strontium fluoride SrF2,
7.50 % of aluminum fluoride AlF3, and
0.53 % of lanthanum fluoride LaF3 ;
Metaphosphate component (b)
9.30 % of aluminum metaphosphate Al(PO3)3,
22.50 % of magnesium metaphosphate Mg(PO3)2, and
14.80 % of barium metaphosphate Ba(PO.sub. 3)2 ;
Barium oxide component (c)
29.20 % of barium oxide BaO; and
Additional oxide component (d)
3.00 % of germanium oxide GeO2.
9. A fluorophosphate glass having an index of refraction ne within the range of from about 1.5753 to about 1.6267, an Abbe number νe within the range of from about 61.4 to about 69.7, and a relatively high positive anomalous partial dispersion, said glass being produced by melting a mixture essentially consisting of the following components, in weight percent:
Fluoride component (a)
0.1% to 1.5% of magnesium fluoride MgF2,
0.1% to 1.5% of calcium fluoride CaF2,
0% to 15.0% of strontium fluoride SrF2,
0% to 25.0% of barium fluoride BaF2,
0% to 10.0% of aluminum fluoride AlF3, and
0.1% to 1.5% of lanthanum fluoride LaF3,
the total sum of the alkaline earth metal fluorides in said mixture not exceeding 38% and the total sum of all fluorides in said mixture not exceeding 45%;
Metaphosphate component (b)
8.0% to 12% of aluminum metaphosphate Al(PO3)2,
3.0% to 25.0% of magnesium metaphosphate Mg(PO3)2, and
10.0% to 18.0% of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture not exceeding 50%;
Barium oxide component (c)
8. 0% to 55.0% of barium oxide BaO;
Additional oxide component (d)
0% to 17.0% of boron trioxide B2 O3,
0% to 10.0% of germanium dioxide GeO2, and
0% to 4.0% of titanium dioxide TiO2.
10. The fluorophosphate glass of claim 9, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0.4% to 0.5% of magnesium fluoride MgF2,
0.5% to 0.6% of calcium fluoride CaF2,
0% to 13.0% of strontium fluoride SrF2,
0% to 22.0% of barium fluoride BaF2,
0% to 8.0% of aluminum fluoride AlF.sub. 3, and
0.5% to 0.6% of lanthanum fluoride LaF3 ;
the total sum of the alkaline earth metal fluorides in said mixture not exceeding the sum of 35% and the total sum of all fluorides not exceeding 43%;
Metaphosphate component (b)
9.0% to 10.0% of aluminum metaphosphate Al(PO3)3,
4.0% to 23.0% of magnesium metaphosphate Mg(PO3)2, and
11.0% to 15.0% of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture not exceeding 47%;
Barium oxide component (c)
10. 0% to 52.0% of barium oxide BaO; and
Additional oxide component (d)
0% of boron trioxide B2 O3,
0% to 8.0% of germanium dioxide GeO2,
0% to 2.0% of titanium dioxide TiO2,
11. The fluorophosphate glass of claim 9, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0.44% of magnesium fluoride MgF2,
0.53% of calcium fluoride CaF2,
0% to 12.2% of strontium fluoride SrF2,
0% to 21.5% of barium fluoride BaF2,
0% to 7.5% of aluminum fluoride AlF3, and
0.53% of lanthanum fluoride LaF3,
the total sum of the alkaline earth metal fluorides being at least 0.97% and not exceeding 34.67% and the total sum of all fluorides in said mixture being at least 1.5% and not exceeding 42.7%;
Metaphosphate component (b)
9.3% of aluminum metaphosphate Al(PO3)3,
4.5% to 22.5% of magnesium metaphosphate Mg(PO3)2, and
11.8% to 14.8% of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture being at least 28.6% and not exceeding 46.6%;
Barium oxide component (c)
10. 7% to 51.9% of barium oxide BaO; and
Additional oxide component (d):
0% to 15.0% of boron trioxide B2 O3,
0% to 7.5% of germanium dioxide GeO2,
0% to 1.5% of titanium dioxide TiO2.
12. The fluorophosphate glass of claim 9, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0.44% of magnesium fluoride MgF2,
0.53% of calcium fluoride CaF2,
12.20% of strontium fluoride SrF2,
7.50% of aluminum fluoride AlF3, and
0.53% of lanthanum fluoride LaF3 ;
Metaphosphate component (b)
9.30% of aluminum metaphosphate Al(PO3)3,
22.50% of magnesium metaphosphate Mg(PO3)2, and
14.80% of barium metaphosphate Ba(PO3)2 ; and
Barium oxide component (c)
32.20% of barium oxide BaO.
13. The fluorophosphate glass of claim 9, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0.44% of magnesium fluoride MgF2,
0.53% of calcium fluoride CaF2,
12.20% of strontium fluoride SrF2,
7.50% of aluminum fluoride AlF3, and
0.53% of lanthanum fluoride LaF3 ;
Metaphosphate component (b)
9.30% of aluminum metaphosphate Al(PO3)3,
22.50% of magnesium metaphosphate Mg(PO3)2, and
14.80% of barium metaphosphate Ba(PO3)2 ;
Barium oxide component (c)
29.20% of barium oxide BaO; and
Additional oxide component (d)
3.00% of germanium oxide GeO2.
14. A fluorophosphate glass having an index of refraction ne, within the range of from about 1.5974 to 1.6915, an Abbe number νe within the range of from about 41.2 to 62.7 and a relatively high positive anomalous partial dispersion, said glass being produced by melting a mixture essentially consisting of the following components, in weight percent:
Fluoride component (a)
0. 1% to 1.5% of magnesium fluoride MgF2,
0.1% to 1.5% of calcium fluoride CaF2,
0% to 15.0% of strontium fluoride SrF2,
0% to 25.0% of barium fluoride BaF2,
0% to 10.0% of aluminum fluoride AlF3, and
0.1% to 1.5% of lanthanum fluoride LaF3,
the total sum of the alkaline earth metal fluorides in said mixture not exceeding 38% and the total sum of all fluorides in said mixture not exceeding 45%;
Metaphosphate component (b)
8.0% to 12% of aluminum metaphosphate Al(PO3)2,
3.0% to 25.0% of magnesium metaphosphate Mg(PO3)2, and
10.0% to 18.0% of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture not exceeding 50%;
Barium oxide component (c)
8.0% to 55.0% of barium oxide BaO;
Additional oxide component (d)
0% to 17.0% of boron trioxide B2 O3,
0% to 10.0% of germanium dioxide GeO2,
0% to 4.0% of titanium dioxide TiO2, and
3.0% to 18.0% of niobium pentoxide Nb2 O5.
15. The fluorophosphate glass of claim 14, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0.44% of magnesium fluoride MgF2,
0.53% of calcium fluoride CaF2,
0% to 12.2% of strontium fluoride SrF2,
0% to 21.5% of barium fluoride BaF2,
0% to 7.5% of aluminum fluoride AlF3, and
0.53% of lanthanum fluoride LaF3,
the total sum of the alkaline earth metal fluorides being at least 0.97% and not exceeding 34.67% and the total sum of all fluorides in said mixture being at least 1.5% and not exceeding 42.7%;
Metaphosphate component (b)
9.3% of aluminum metaphosphate Al(PO3)3,
4.5% to 22.5% of magnesium metaphosphate Mg(PO3)2, and
11.8% to 14.8% of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture being at least 28.6% and not exceeding 46.6%;
Barium oxide component (c)
32.2% of barium oxide BaO; and
Additional oxide component (d)
0% to 15.0% of boron trioxide B2 O3,
0% to 15.0% of boron trioxide B2 O3,
0% to 7.5% of germanium dioxide GeO2,
0% to 1.5% of titanium dioxide TiO2, and
3.0% to 18.0% of niobium pentoxide Nb2 O5.
16. The fluorophosphate glass of claim 15, in which the mixture consists of the following components, in weight percent:
Fluoride component (a)
0.44% of magnesium fluoride MgF2,
0.53% of calcium fluoride CaF2,
12.20% of strontium fluoride SrF2,
7.5% of aluminum fluoride AlF3, and
0.53% of lanthanum fluoride LaF3 ;
Metaphosphate component (b)
9.3% of aluminum metaphosphate Al(PO3)3,
4.5% to 22.5% of magnesium metaphosphate Mg(PO3)2, and
11.8% to 14.8% of barium metaphosphate Ba(PO3)2,
the total sum of the metaphosphates in said mixture being at least 28.6% and not exceeding 46.60%;
Barium oxide component (c)
32.2% of barium oxide BaO; and
Additional oxide component (d)
3.0% to 18.0% of niobium pentoxide Nb2 O5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732342484 DE2342484B2 (en) | 1973-08-23 | 1973-08-23 | METHOD OF MANUFACTURING A FLUOROPHOSPHATE GLASS HAVING A REFRACTORY INDUSTRY N DEEP E GREATER THAN 1.57, AN ABBE VALUE NY DEEP E SMALLER THAN 70 AND A RELATIVELY HIGH POSITIVE ABNORMAL PARTIAL DISPERSION |
| DT2342484 | 1973-08-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3954484A true US3954484A (en) | 1976-05-04 |
Family
ID=5890452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/499,661 Expired - Lifetime US3954484A (en) | 1973-08-23 | 1974-08-22 | Fluorophosphate glass and process of making same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3954484A (en) |
| JP (1) | JPS5328169B2 (en) |
| DE (1) | DE2342484B2 (en) |
| FR (1) | FR2241505B3 (en) |
| GB (1) | GB1435868A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040846A (en) * | 1975-03-29 | 1977-08-09 | Ernst Leitz G.M.B.H. | Optical fluorophosphate glass and process of making same |
| US4115131A (en) * | 1976-04-30 | 1978-09-19 | Nippon Kogaku K.K. | Optical glass |
| US4213788A (en) * | 1978-03-30 | 1980-07-22 | Fuji Photo Film Co., Ltd. | Fluoride and phosphate containing optical glass |
| US4285730A (en) * | 1979-10-05 | 1981-08-25 | Corning Glass Works | Moldable glasses |
| US4309078A (en) * | 1979-05-15 | 1982-01-05 | Minolta Camera Kabushiki Kaisha | Pentagonal prism for camera viewfinder |
| US4386163A (en) * | 1981-01-20 | 1983-05-31 | Nippon Kogaku K.K. | Fluorophosphate optical glass |
| US4433062A (en) * | 1982-06-04 | 1984-02-21 | Corning Glass Works | Moldable fluorophosphate glasses containing Nb2 O5 |
| US4849002A (en) * | 1987-10-27 | 1989-07-18 | Kigre, Inc. | Ion-exchangeable germanate method for strengthened germanate glass articles |
| US4915721A (en) * | 1985-10-19 | 1990-04-10 | Ernst Leitz Wetzlar Gmbh | Process for preparation of fluorophosphate optical glass |
| US5735920A (en) * | 1993-06-08 | 1998-04-07 | Canon Kabushiki Kaisha | Method of manufacturing optical glass element |
| US6495481B1 (en) * | 2001-05-21 | 2002-12-17 | Nano Technologies | Glasses for laser and fiber amplifier applications and method for making thereof |
| CN108529874A (en) * | 2017-03-02 | 2018-09-14 | Hoya株式会社 | Optical glass and optical element |
| WO2018212638A3 (en) * | 2017-05-19 | 2019-02-21 | 한국광기술원 | Fluorophosphate-based glass for active element |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3037004A1 (en) * | 1979-10-05 | 1981-04-16 | Corning Glass Works, Corning, N.Y. | FOR LOW TEMPERATURES MOLDABLE GLASS |
| DE3634674A1 (en) * | 1985-10-19 | 1987-04-23 | Leitz Ernst Gmbh | OPTICAL FLUORPHOSPHATE GLASS WITH ANOMAL POSITIVE PARTIAL DISPERSION AND METHOD FOR THE PRODUCTION THEREOF |
| DE3634675A1 (en) * | 1985-10-19 | 1987-04-23 | Leitz Ernst Gmbh | OPTICAL PHOSPHATE GLASS WITH ANOMAL POSITIVE PARTIAL DISPERSION AND METHOD FOR THE PRODUCTION THEREOF |
| TWI687385B (en) * | 2017-03-31 | 2020-03-11 | 日商Ｈｏｙａ股份有限公司 | Optical glass and optical components |
| JP6606568B2 (en) * | 2017-03-31 | 2019-11-13 | Ｈｏｙａ株式会社 | Optical glass and optical element |
| JP6985173B2 (en) * | 2018-02-14 | 2021-12-22 | 光ガラス株式会社 | Optical glass, optical elements, optical systems, interchangeable lenses for cameras and optical devices |
| TWI714082B (en) * | 2018-05-10 | 2020-12-21 | 日商Ｈｏｙａ股份有限公司 | Optical glass and optical components |
| CN111138082B (en) * | 2020-01-13 | 2022-06-17 | 苏州众为光电有限公司 | High-stability glass optical fiber and preparation method thereof |
| JP7090678B2 (en) * | 2020-10-28 | 2022-06-24 | Hoya株式会社 | Optical glass and optical elements |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2430539A (en) * | 1946-01-29 | 1947-11-11 | Eastman Kodak Co | Titanium fluophosphate glass |
| US2901363A (en) * | 1948-07-27 | 1959-08-25 | American Optical Corp | Glass compositions and method of making same |
| US2919201A (en) * | 1958-07-22 | 1959-12-29 | Director Of The Agency Of Ind | Optical glass |
| US2996391A (en) * | 1953-01-21 | 1961-08-15 | Leitz Ernst Gmbh | Optical glass |
| US3068108A (en) * | 1958-02-05 | 1962-12-11 | Jenaer Glaswerk Schott & Gen | Optical type glass compositions with high fluorine and titanium content |
| US3492136A (en) * | 1965-12-31 | 1970-01-27 | Leitz Ernst Gmbh | Fluorophosphate optical glass and method of preparing the same |
| US3508937A (en) * | 1966-06-25 | 1970-04-28 | Leitz Ernst Gmbh | Fluorophosphate glass |
| US3597245A (en) * | 1967-10-28 | 1971-08-03 | Leitz Ernst Gmbh | Phosphate optical glass with positive anomalous partial dispersion |
| US3656976A (en) * | 1969-05-24 | 1972-04-18 | Haya Glass Works Ltd | Stable fluorophosphate optical glass |
| US3671276A (en) * | 1968-06-27 | 1972-06-20 | Leitz Ernst Gmbh | Optical fluorophosphate glass having an anomalous partial dispersion ratio |
| US3847624A (en) * | 1972-06-26 | 1974-11-12 | Leitz Ernst Gmbh | Fluorophosphate optical glass |
-
1973
- 1973-08-23 DE DE19732342484 patent/DE2342484B2/en not_active Withdrawn
-
1974
- 1974-08-12 JP JP9160874A patent/JPS5328169B2/ja not_active Expired
- 1974-08-22 US US05/499,661 patent/US3954484A/en not_active Expired - Lifetime
- 1974-08-22 FR FR7428845A patent/FR2241505B3/fr not_active Expired
- 1974-08-22 GB GB3689574A patent/GB1435868A/en not_active Expired
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2430539A (en) * | 1946-01-29 | 1947-11-11 | Eastman Kodak Co | Titanium fluophosphate glass |
| US2901363A (en) * | 1948-07-27 | 1959-08-25 | American Optical Corp | Glass compositions and method of making same |
| US2996391A (en) * | 1953-01-21 | 1961-08-15 | Leitz Ernst Gmbh | Optical glass |
| US3068108A (en) * | 1958-02-05 | 1962-12-11 | Jenaer Glaswerk Schott & Gen | Optical type glass compositions with high fluorine and titanium content |
| US2919201A (en) * | 1958-07-22 | 1959-12-29 | Director Of The Agency Of Ind | Optical glass |
| US3492136A (en) * | 1965-12-31 | 1970-01-27 | Leitz Ernst Gmbh | Fluorophosphate optical glass and method of preparing the same |
| US3508937A (en) * | 1966-06-25 | 1970-04-28 | Leitz Ernst Gmbh | Fluorophosphate glass |
| US3597245A (en) * | 1967-10-28 | 1971-08-03 | Leitz Ernst Gmbh | Phosphate optical glass with positive anomalous partial dispersion |
| US3671276A (en) * | 1968-06-27 | 1972-06-20 | Leitz Ernst Gmbh | Optical fluorophosphate glass having an anomalous partial dispersion ratio |
| US3656976A (en) * | 1969-05-24 | 1972-04-18 | Haya Glass Works Ltd | Stable fluorophosphate optical glass |
| US3847624A (en) * | 1972-06-26 | 1974-11-12 | Leitz Ernst Gmbh | Fluorophosphate optical glass |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040846A (en) * | 1975-03-29 | 1977-08-09 | Ernst Leitz G.M.B.H. | Optical fluorophosphate glass and process of making same |
| US4115131A (en) * | 1976-04-30 | 1978-09-19 | Nippon Kogaku K.K. | Optical glass |
| US4213788A (en) * | 1978-03-30 | 1980-07-22 | Fuji Photo Film Co., Ltd. | Fluoride and phosphate containing optical glass |
| US4309078A (en) * | 1979-05-15 | 1982-01-05 | Minolta Camera Kabushiki Kaisha | Pentagonal prism for camera viewfinder |
| US4285730A (en) * | 1979-10-05 | 1981-08-25 | Corning Glass Works | Moldable glasses |
| US4386163A (en) * | 1981-01-20 | 1983-05-31 | Nippon Kogaku K.K. | Fluorophosphate optical glass |
| US4433062A (en) * | 1982-06-04 | 1984-02-21 | Corning Glass Works | Moldable fluorophosphate glasses containing Nb2 O5 |
| US4915721A (en) * | 1985-10-19 | 1990-04-10 | Ernst Leitz Wetzlar Gmbh | Process for preparation of fluorophosphate optical glass |
| US4849002A (en) * | 1987-10-27 | 1989-07-18 | Kigre, Inc. | Ion-exchangeable germanate method for strengthened germanate glass articles |
| US5735920A (en) * | 1993-06-08 | 1998-04-07 | Canon Kabushiki Kaisha | Method of manufacturing optical glass element |
| US6495481B1 (en) * | 2001-05-21 | 2002-12-17 | Nano Technologies | Glasses for laser and fiber amplifier applications and method for making thereof |
| CN108529874A (en) * | 2017-03-02 | 2018-09-14 | Hoya株式会社 | Optical glass and optical element |
| WO2018212638A3 (en) * | 2017-05-19 | 2019-02-21 | 한국광기술원 | Fluorophosphate-based glass for active element |
| US10988406B2 (en) | 2017-05-19 | 2021-04-27 | Korea Photonics Technology Institute | Fluorophosphate glasses for active device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5328169B2 (en) | 1978-08-12 |
| FR2241505A1 (en) | 1975-03-21 |
| GB1435868A (en) | 1976-05-19 |
| JPS5050416A (en) | 1975-05-06 |
| DE2342484B2 (en) | 1977-12-29 |
| DE2342484A1 (en) | 1975-03-20 |
| FR2241505B3 (en) | 1977-06-17 |
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